Nondiffusing sulphonamide coupler for color photography



Patentemfict. 1942 ED STATES. PATENT-ferries "2.29am v 7' NDNDIFFUSINGSULPHONAMIDE COUPLER FOB PHOTOGRAPHY Arnold Weissberger, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporationor New'Jersey No Drawing. Application. August 22, 1940, Serial No.353,669. 151 Great 31-min August 24, 1939 8 Claims. (01. 95-6) Thisinvention relates to photographic color forming compounds andparticularly to non-diffusing coupler compounds containing sulphonamidegroups for incorporation in photographic emulsion layers. a v

Color forming compounds which react with the development product ofaromatic amino developing agents to form colored images on photographicdevelopment have been the subject of numerous prior patents. The dyesformed in this way are insoluble in water and in the ordi-' naryphotographic developing and fixing baths although the silver imagesformed simultaneously with them duringthe photographic development maybe removed from the photographic layer to leave pure dye images in thelayer. Such a compound which is employed in conjunction with thedeveloping agent for the silver and which couples with the developmentproduct of the developer during photographic development is referred toherein as a coupling component or coupler. ,When these couplingcomponents are incorporated in the photo-.

. graphic layer prior tofexposure', they do not af- 3 In Vittum,Peterson and Porter U. S. Patent N0. 2,271,238, granted January 27, 1942, coupling components are described which contain sulphonamide groups.Such couplers are desirable by reason of their. solubilitycharacteristics and the improved properties of the dyes formed fromthem. The couplers described in theVittmn,

Peterson andPorter'application-main general,

soluble in the developing solution and not suitable for use in theemulsion layer because of 40 their'tendency to fiuse from the layer. Thedyes formed fromt ese couplers, however, have better light transmissioncharacteristics and are more stable tolleat and light than the dyesproduced from PIEY1OIIS1Y known coupling compo- 45 nents It is an objectof the present invention to provide coupling components which have thedesirable properties oi couplers containing the sulphonamidekroup butwhich may b mm o. 50 rim-oo-cm-co-mm rated in photogfaphicjemulsionlayers as nondiflusing compounds. A further object is tov provide novelphotographic couplers having desizable properties with respect to heatand light stability. .A still further object is to provide 55photographic couplers which form image dyes having desirable lighttransmission characteris to form a dye.

tics. Other objects will appear from the following description of myinvention.

These objects are acegmplished by replacing the free hydrogen atom ofthe sulphonamide group otcouplers containing such group with A radicalshaving the property of rendering the couplers non-diffusing'in gelatinor other col:

loidal media. a

The color forming or coupling compounds which I have-found to besuitable for incorporastructure where R is an aryl radical such asphenyl or naphthyl which may be substituted but which, may not be ahydroxy substituted aryl radical,

X is an alkyl or phenyl substituted alkyl which may be substituted and Yis an organic substitu- 1 ent such as alkyl or arylradicals.

The coupler must also contain a group reactive with the oxidationproduct of the developer This group is the reactive methylene orethenolgroup characteristicof couapler compounds and wil1.be more specificallyreferred to hereinafter. In the case of a reac-. tive methylene group itmay be contained in the portion' oi the molecule attached either to thesulphur or to the nitrogen atom of the sulphonamide group. In the caseof the reactive ethenol group this group may not be attached directly tothe sulphur atom of the sulphonamide but may be attached to the nitrogenatom or to one of the groups attached to the nitrogen atom oi thesulphonamide radical. As pointed out in the Vittum, Peterson and PorterPatent nol group attached to the-sulphur atom of the sulphonamideproduce dyes which are less sta-= ble to heat and light than compoundshaving the ethenol group attached to the nitrogenatom of thesulphonamide group or having a reactive methylene group attached .eitherto the sulphur atom or to the nitrogen atom.

My invention may be illustrated by reference to the following compoundsI and n. I

un-co-cm-oo-cgr,

cm r

onus-car o -r r-crm couplers according Compound -I is a coupler capableof producing a yellow dye image and is of the type described in Vittum,Peterson and Porter U. 8. Patent No.

2,271,238. It'is soluble in photographic develop-' ing solutions.Compound II is identical with compound 1 except that the free hydrogenatom of the sulphonamide group has been replaced with a methyl radical.Compound II also produces a yellow dye upon development with the properphotographic developing agent. How ever, because of the replacement ofthe hydrogen atom oi the sulphonated group witha suitable radical, theoouplerisno longer soluble in the developer but maybe incorporated in .aphotographic emulsion layer as a non-diffusing 'compound. My inventionresides in the discoveryb-lN-(benryl)-a-naphthalene-sulpbonylaminol-l-naphthol I Ill ' that, bythe substitution of'this i'ree hydrogen atom of the sulphonamide groupwith suitable organic radicals, the valuable properties of the I on-2,4-dichloro-6-[N-(benzyn-p-nlphthaleno-sulphonylaminol-lnlphthol on.

hHn I t-amyldiplienylothei'siflpbonylamino-l-naphthol2,4-dibromo-6-[N-(benzylyfi-nzphthalenc-sulphonyleminol-lm tho!z-monochlorwlN-(bonzylgpr i: lghalen o-sulphonylaminol-l- .411" I B-lN(p any prom-mphw phanygaminoh naphthol tmcm i-mmnmm .o-cmcm cm y N-O: vNHooomcoOocm t-CtHu N-(p-anisoylacetaminobenzenesul honyD-N-('-pbenylpropyl)-pm tert.-amy

be attached to the sulphur atom of the sulphonamide group but only tothe nitrogen atom as illustrated, for example, by compounds 1 to- 11. ifthe reactive portion of the coupler is of the tion of the moleculeattached to the sulphur atom of the sulphonamide group as illustrated,for example; by compounds 12. to 37 or in the portion of the moleculeattached to the nitrogen atom of the sulphonamide group as illustratedby com-' pound as. I c I One of the substituents on the nitrogen atomtion in the amino group as well as in the ring, such as'alkylphenylenediamines and aliwltoluaylenediamines. These compounds areusually used in the salt form, such as the hydrochloride or thesulphate, which are more stable than the amines themselves. Suitablecompounds are diethyl-p-phenylenediamine hydrochloride, men--omethyl-p-phenylenediaminehydrochloride, dimethyl pphenylenediaminehydrochloride a n d dimethyl-p-phenylenediaminesulphate. The paminophenols and their substitution products may also beused where the amino group is unsubstituted. All of these compounds havean unsubstituted amino group which enables the oxidation products of thedeveloper to couple with I the color forming compounds to form a dyeimage.

'25 methylene type, it may be contained in the por'-' made according tomy invention;

Errample 1 p-Aminodiethylaniline sulphategrams 2.5 Sodium sulphiteanhydrous do-. 2 Sodium carbonatev anhydrous do-. :20 Potassium brom ded 1 Water t HYPIZ- 1 Example 2 p-Aminodiethylaniline hydrochloridegrams" 2 Sodium sulphite anhydrous ..do 5 Sodium carbonate anhydrousdo.. 20 Potassium bromide do- 2 Water to liter 1 of the sulphonamidegroup, that is, Y in the general formula above, may be any organicsubstituent such as an alkyl or an aryl radical. This substituent may ormay not be a phenolic hydroxyl radical. The other substituent onthenitrogen atom, that is, X in the general formula above, is limited toalkyl, phenyl substituted alkyl or benzyl radicals.- This is thesubstituent which controls the solubility of the coupler and producesthe property of non-diffusibility ingelatin. This substituent may be asimple-methyl or ethyl radical or a phenyl substituted alkyl radicalsuch as benzyl or v-phenylpropyl. These radicals obviously may beconsidered phenyl substituted alkyl radicals, benzyl being aphenylvsubstituted methyl radical and q-phenylpropyl being a phenylsubstituted propyl radical.

As stated above the coupler must contain the functional or reactivegroup common to color forming compounds which react with primaryaromatic amino developing-agents. This reactive group takes the form ofa reactive methylene or reactive etlrenol group. By reactive methylenewe mean a CH: group which is reactive in the coupling proces's.j The cmgroup is usually present betweentwo negative centers as in'the groups or-CO-CH2-CN.

One of the hydrogen atoms of the methylene.

position of the hydroxyl group.-

The aromatic amino developing agents used; with the coupler compounds ofmy invention 111* 1' clude the mono-, diand tri-aminoaryl compounds andtheir derivativesformed by substitu- The following examples areillustrative of developing solutions which may be used to developemulsion layers containing the couplers The couplers used according tomy invention may be incorporated in silver halide emulsion alcohol andadd this to the emulsion. For example, '3 grams of coupler may bedissolved or suspended in cc. of ethyl alcohol and sodium hydroxideadded in the amount of 1 /2 equivalent weights of the coupler. Thesodium'hydroxide maybe added as solid or as a concentrate solugeneratedin a solution of 50 cc.'of alcohol and this solution is addedto 1 literof a gelatin silver then be adjusted if desired by adding a suitableacid such as acetic or sulphuric acid to neutralize all or part of thesodium hydroxide used to form the sodium salt of the coupler.

' The coupling components may be incorporated either in gelatin or inother colloidal materials such as collodion, organic esters of celluloseor synthetic resins. The emulsion may be carried by a transparent mediumsuch as glass, cellulose esters, or synthetic resin or a non-transparentreflecting medium such as paper or an opaque cellulose ester. Theemulsion may be coated'as a single layer on the support or superposedlayers containing the couplers may be coated on one or both sides of thesupport. The superposed layers may be differentially. sensitized for theformation of anatural colorimage in the well known mane ner.' v

The examples and compounds set forth in the present specification areillustrative only audit is to be understood that my invention is to betaken as limited only by the scope of' the ap-' .pended claims.

I claim: 1. A photographic emulsion for forming colored imagescomprising a colloidal carrier 6 containing a Sensitive silver halideand a coupler compound having the formula:

, I x 'n-soi-N where R is an aryl radical other than a hydro substitutedaryl radical, x is a phenyl substituted alkyl radical and Y is selectedfrom the class consisting of alkyl and aryl radicals, said couplercompound'containing at least one group selected from the classconsisting of. methylene and ethenol which is reactive with primaryaromatic amino developers.

2. A photographic emulsion for forming colored images comprising acolloidal carrier containing a sensitive silver halide and acouplercompound having the formula:

I olk- 0H;

R-SOz-N Y where R is an aryl radical other than a hydroxy substitutedaryl radical and Y- is selected from the class consisting of alkyl andaryl radicals, said coupler compound containing at least one .groupselected from theclass consisting of methylene and ethenol which isreactive with 1 I aromatic amino developers.

3. A photographic emulsion for forming colored images comprising acolloidal carrier containing a sensitive silver halide and a coupler 7compound having the formula: 1

I where R is an aryl radicalother than a hydroxy substituted arylradical and Y is selected from the class consisting of alkyl and arylradicals, said coupler compound containing at least one group selectedfrom the class consisting of methylene'and ethenol which is reactivewith aromatic amino developers. 4. A photographic emulsion for formingcolored images comprising a colloidal carriercontaining a sensitivesilver halide and acoupler compound having the formula: t i

R-SQr-N where R is an aryl radical other than a hydroxy substituted arylradical, X is selected from the class consisting of alkyl and phenylsubstituted alkyl radicals andZ is anaphthol residue, said couplercompound containing at least one group selected from the classconsisting of methylene and ethenol which is reactive with primaryaromatic photographic developers.

5. In-the method of producing a colored photographic image in a gelatinosilver halide emulsion layer, the step which comprises treating theexposed layer containing a coupler compound having the formula:

BSOIN accen s whereR is an aryl radical'other than ahydroxy substitutedaryl radical, x is a phenyl substituted alkyl radical and Y is selectedfrom the class consisting of alkyl and aryl radicals, said couplercompound containing at least one group selected from the classvconsisting of methylene and ethenol which is reactive with primaryaromaticamino developers with a developer containing a primary aromaticamino developing agent.

6. In the method of producing a colored pho-' tographic image in agelatino silver halide emulsion layer, the step which comprises treatingthe exposed layer containing a coupler compound having the formula:

CHi-CcHs R-so,-N

where R is an aryl radical other than a hydroxy substituted aryl radicaland Y is selected from the class consisting of alkyl and-aryl radicals,said coupler compound containing at least one group selected from theclass consisting of methylerie and ethenol which is reactive withprimary aromatic amino developers, with a developing solution containinga primary aromatic ami-.

no developing agent,

7. In the method. of producing'a colored photographic image in agelatino silver halide emulsion layer, the step which comprises treatingthe exposed layer containing a coupler compound having the formula: I

' CaHc-CsHn R-SOa-N where R is an aryl radical other than a hydroxysubstituted aryl radical and Y is selected from the class consisting ofalltyl and aryl radicals, said coupler compound containing at least onegroup selected from the class consisting of methylene and ethenol whichis reactive with primary amwhere R is an aryl radical other than ahydroxy substituted aryl radical, X is selectedirom the class consistingof alkyl and phenyl substituted alkyl radicals and Z is a. naphtholresidue, said coupler compound containing at least one group selectedfrom the class consisting of methylene and ethenol which is reactivewith primary aromatic amino developers, with a developing solutioncontaining a primary aromatic amino developing agent. v

' ARNOLD WEISSBERGER.

